Urea Oxidation Research Articles

Urea assimilation and oxidation support activity of phylogenetically diverse microbial communities of the dark ocean.

Urea is hypothesized to be an important source of nitrogen and chemical energy to microorganisms in the deep sea; however, direct evidence for urea use below the epipelagic ocean is lacking. Here, we explore urea utilization from 50 to 4000 meters depth in the northeastern Pacific Ocean using metagenomics, nitrification rates, and single-cell stable-isotope-uptake measurements with nanoscale secondary ion mass spectrometry. We find that on average 25% of deep-sea cells assimilated urea-derived N (60% of detectably active cells), and that cell-specific nitrogen-incorporation rates from urea were higher than that from ammonium. Both urea concentrations and assimilation rates relative to ammonium generally increased below the euphotic zone. We detected ammonia- and urea-based nitrification at all depths at one of two sites analyzed, demonstrating their potential to support chemoautotrophy in the mesopelagic and bathypelagic regions. Using newly generated metagenomes we find that the ureC gene, encoding the catalytic subunit of urease, is found within 39% of deep-sea cells in this region, including the Nitrososphaeria (syn., Thaumarchaeota; likely for nitrification) as well as members of thirteen other phyla such as Proteobacteria, Verrucomicrobia, Plantomycetota, Nitrospinota, and Chloroflexota (likely for assimilation). Analysis of public metagenomes estimated ureC within 10-46% of deep-sea cells around the world, with higher prevalence below the photic zone, suggesting urea is widely available to the deep-sea microbiome globally. Our results demonstrate that urea is a nitrogen source to abundant and diverse microorganisms in the dark ocean, as well as a significant contributor to deep-sea nitrification and therefore fuel for chemoautotrophy.

Synergetic Modulation of Electronic Properties of Cobalt Oxide via "Tb" Single Atom for Uphill Urea and Water Electrolysis.

Exploring single-atom (SA) catalysts in hybrid urea-assisted water electrolysis offers a viable alternative to both Hydrogen (H2) generation and polluted water treatment. However, the unfavorable electronic stabilization, low SA content, intrinsically slow kinetics, and imbalanced adsorption-desorption steps are the bottleneck for its scale-up implementation. Herein, a rare-earth Terbium single atom (TbSA) is topologically stabilized on defect-rich Co3O4 (TbSA@d-Co3O4) by Tb─O co-ordination for urea oxidation reaction (UOR) and H2 evolution reaction (HER). Benefitting from the strong TbSA interaction with the d-Co3O4, the TbSA@d-Co3O4 achieves a 10mAcm-2 current density at 1.27V and -35mV for UOR and HER, respectively. Remarkably, when TbSA@d-Co3O4 is applied as a bi-functional catalyst in a two-electrode system, it merely requires 1.22V to acquire 10mAcm-2 with excellent operational stability for 100 h. The hybrid electrolyzer can be successfully empowered by the triboelectric nanogenerator, AA battery, and solar panel with a nominal potential of 1.5V. The mechanistic investigation predicts "TbSA" insertion in d-Co3O4 lowered the potential determining step, attributed to balanced reaction energetics for adsorption-desorption of intermediates and favorable charge transfer characteristics for UOR. This work offers a new paradigm to explore the catalytic properties of rare-earth "f-block" elements to create advanced electrocatalysts via structural modulation.

Ultra-fast synthesis of transition metal-MXene nanocomposite electrocatalyst for energy-saving seawater hydrogen production: Experiment and theory

Switching from the urea oxidation reaction (UOR) to the oxygen evolution reaction (OER) is a beneficial way to lower the amount of energy needed to make hydrogen gas during the hydrogen evolution reaction (HER). Due to the sluggish reaction kinetics of the six electrons reaction of UOR, designing a privileged bifunctional electrocatalyst for both HER and UOR necessitates. The 2D nano-sized non-noble metal electrocatalysts make it possible to speed up reactions and improve their electrocatalytic performance. We synthesized nickel-cobalt-MXene composite nanosheets (NiCoMXene) on the surface of copper foam using a one-pot, simple, and ultra-fast electrochemical method. This 2D electrocatalyst demonstrates high electrocatalytic performance towards HER (overpotential of 76 mV at −10 mA cm−2) with excellent durability in alkaline media. Furthermore, NiCoMXene nanocomposite served as a bifunctional electrocatalyst to investigate hydrogen gas production by a hybrid system HER coupled with UOR in seawater. The NiCoMXene requires a low overpotential for HER (81 mV) and UOR (1.38 V) to achieve a current density of 10 mA cm−2 in seawater, and the needed cell voltage to reach the same current density is 1.42 V in seawater. Our DFT analysis found a significant synergy between MXene and NiCo in the electrocatalyst. PDOS analysis showed remarkably that introducing Ni atoms to MXene shifts the d-band center to the left (lower energy), while Co atoms shifts it to the right (higher energy) and increased states near the Fermi level. This electronic structure makes the nanocomposite an ideal electrocatalyst, with MXene providing electrons and Co atoms serving as active sites for both HER and UOR.This research work can provide a useful directive to explore the electrocatalysts with outstanding catalytic activity.

3D NiCoW Metallic Compound Nano-Network Structure Catalytic Material for Urea Oxidation

Urea shows promise as an alternative substrate to water oxidation in electrolyzers, and replacing OER with the Urea Oxidation Reaction (UOR, theoretical potential of 0.37 V vs. RHE) can significantly increase hydrogen production efficiency. Additionally, the decomposition of urea can help reduce environmental pollution. This paper improves the inherent activity of catalytic materials through morphology and electronic modulation by incorporating tungsten (W), which accelerates electron transfer, enhances the electronic structure of neighboring atoms to create a synergistic effect, and regulates the adsorption process of active sites and intermediates. NiCoW catalytic materials with an ultra-thin nanosheet structure were prepared using an ultrasonic-assisted NaBH4 reduction method. The results show that during the OER process, NiCoW catalytic materials have a potential of only 1.53 V at a current density of 10 mA/cm2, while the UOR process under the same conditions requires a lower potential of 1.31 V, demonstrating superior catalytic performance. In a mixed electrolyte of 1 M KOH and 0.5 M urea, overall water splitting also shows excellent performance. Therefore, the designed NiCoW electrocatalyst, with its high catalytic activity, provides valuable insights for enhancing the efficiency of water electrolysis for hydrogen production and holds practical research significance.

Fe-Doped Ni3S2 Induces Self-Reconstruction for Urea-Assisted Water Electrolysis Enhancement.

Urea oxidation reaction (UOR) is an attractive alternative anodic reaction to oxygen evolution reaction (OER) for its low thermodynamic potential (0.37 V vs RHE). A major challenge that prohibits its practical application is the six-electron transfer process during UOR, demanding enhancements in the catalytic activity. Herein, a Fe-doped Ni3S2 catalyst with a uniform flower-like structure is synthesized in situ on nickel foam via a simple one-step hydrothermal method. The electrochemical properties of Fe-Ni3S2 are significantly improved since a current density of 10 mA cm-2 only requires a 1.33 V potential and remains stable for 60 h. The structural characterization demonstrates a strong interaction between Fe and Ni3S2. After Fe doping, the active site increases, which promotes the formation of NiOOH on the catalyst surface, thus speeding up the UOR process. These changes are beneficial to charge transfer and optimize the adsorption energy of the intermediates. In situ EIS further confirms that Fe promotes electron transfer during the UOR process, reduces the interface resistance between the catalyst and the electrolyte, and lowers the driving voltage.

Insight into the High Activity of Nickel Phosphide Precatalysts for Urea Oxidation

Insight into the High Activity of Nickel Phosphide Precatalysts for Urea Oxidation

Utilizing cationic vacancies to enhance nickel-cobalt layered double hydroxides for efficient electrocatalytic urea oxidation reaction

Electrocatalytic urea oxidation reaction (UOR) is a promising approach for urea-rich wastewater splitting, which benefits for reducing energy consumption in hydrogen production accompanying environmental protection and sustainable energy development. To address the limitations posed by the self-oxidation of nickel-based catalysts on the activity of UOR, we here developed a NiCo LDH nanosheet catalyst with abundant Ni vacancies to initiate the UOR process prior to nickel oxidation. Electrochemical impedance spectroscopy and In-situ spectroscopic characterizations confirm that the UOR process primarily occurs on the surface of the catalyst, rather than being driven by nickel oxidation products. The favorable electronic structure modulation induced by Ni vacancies makes the catalyst more energetically favorable for the UOR compared to nickel self-oxidation. The catalyst exhibits excellent UOR activity, only requiring 1.27 V vs. RHE at 10 mA cm−2 and 1.34 V vs. RHE at 100 mA cm−2, with no significant decay observed after over 120 h of operation. Furthermore, it can function as a bifunctional catalyst, requiring only 1.66 V to achieve 100 mA cm−2 for the UOR||HER system. This study expands the pathway for the application of cationic vacancies in UOR.

Regulating the electronic structure of Ni3Se4-MoSe2 by coupling with ZIF-derived Co@C promotes boosted urea-assisted water splitting at industrial current density

Adopting urea oxidation reaction (UOR) as an alternative to oxygen evolution reaction (OER) is a prospective approach to achieve energy-saving H2 generation as well as purify wastewater with abundant urea, while the industrial application of bifunctional catalysts for hydrogen evolution reaction (HER) and UOR still remains challenge. Herein, novel coleslaw-like arrays Ni3Se4-MoSe2/Co@C electrocatalyst is fabricated by coupling Ni3Se4-MoSe2 heterointerface with Co-ZIF derived Co@C, in which the synergistic effects of Ni3Se4-MoSe2 and Co@C can tailor the electronic state caused by Ni, Mo, Se and Co atoms, contributing to the modulated d-band center and charge redistribution, hence balancing the absorption and desorption of HER and UOR reaction intermediates and realizing facilitated HER and UOR activities. Furthermore, the coleslaw-like arrays could expose more active sites as well as speed up mass transport. As a result, Ni3Se4-MoSe2/Co@C shows ultralow potentials of 189 mV and 1.427 V to achieve industrial current density of 1000 mA·cm−2 with small Tafel slopes of 56.5 and 30.2 mV·dec-1 towards HER and UOR with exceptional long durability, respectively. Impressively, a remarkably decreased cell voltage of 1.98 V is seen to achieve 1000 mA·cm−2 for urea-assisted water splitting. This study introduces a new strategy to producing non-noble-based selenides with ZIF derivative to realize bifunctional application in energy-saving H2 production with industrial treatment of urea wastewater.

Interface engineering in Ni(OH)2/NiOOH heterojunction to enhance energy-efficient hydrogen production via urea electrolysis

Electrochemical urea electrolysis has merged as a promising alternative to conventional water splitting methods for hydrogen fuel production due to its cost-effectiveness and superior energy efficiency. The utilization of heterostructures has been proposed as a viable strategy to improve the efficiency of the urea oxidation reaction (UOR) by augmenting the quantity of active sites and optimizing the electronic structure. In this study, a Ni(OH)2/NiOOH heterojunction, referred to as H-Ni, was synthesized via a straightforward hydrothermal synthesis method. The notable performance of H-Ni in UOR is ascribed to the synergistic interaction between Ni(OH)2 and NiOOH, which constitute the principal components of the catalyst. Density functional theory (DFT) calculations reveal that the H-Ni composite is capable of modulating the d-band center, thereby enhancing the adsorption and desorption of reaction intermediates and decreasing the Gibbs free energy (ΔG) associated with the rate-determining step (RDS) of the UOR. Experimental results from catalytic performance tests indicate that the H-Ni-140 catalyst attains a current density of 10 mA·cm−2 in 1 a M KOH electrolyte containing 0.33 M urea at a relatively low potential of 1.341 V versus reversible hydrogen electrode (RHE), thereby highlighting its superior electrocatalytic performance. Furthermore, the catalyst requires only a cell voltage of 1.78 V to achieve a current density of 100 mA·cm−2, which is approximately 120 mV lower than that required for water electrolysis. This work presents a straightforward methodology for the cost-effective development of heterojunction catalysts.

One-Pot Fast Electrochemical Synthesis of Ternary Ni-Cu-Fe Particles for Improved Urea Oxidation

The climate crisis has become the most serious concern of human beings and environments worldwide in the 21st century. Global concerns about cancer epidemiology mainly originate from anthropogenic activities, particularly fossil-based operations. A key solution to this problem is the use of fuel cells—devices—capable of the direct conversion of fuel chemical energies like urea into electricity. To make their commercialization reasonable, one of the problems that needs to be solved is the development of anodic materials. The majority of investigations on urea oxidation are based on nickel, but its inadequate activity limits the efficiency of these devices. In this work, we propose and synthesize a Ni-Cu-Fe ternary electrocatalyst for urea oxidation through a fast and facile electrodeposition method. The properties of the synthesized material are examined by Scanning Electron Microscopy (SEM) conjugated with Energy Dispersive X-ray Spectroscopy (EDS), Transmission Electron Microscopy (TEM), and X-ray Diffraction (XRD). Its electrochemical properties were also examined in a 1 M KOH solution with and without 0.15 M urea. We found that the prepared powder is active in the electro-oxidation of urea, with 1.65 Vvs RHE required for a current density of 10 mA cm−2 and a stable potential of 2.38 Vvs RHE required for 3 h of polarization at 10 mA cm−2.

Novel Gel method MXene-Supported Dual-Site PtNi-NiO for Electrocatalytic Water Reduction and Urea Oxidation.

Compared to the traditional oxygen evolution reaction (OER), the urea oxidation reaction (UOR) generally exhibits a lower overpotential during the electrolytic process, which is conducive to the hydrogen evolution reaction (HER) at the cathode. The superior structure and abundant sites play a crucial role in promoting the adsorption and cleavage of urea molecules. Therefore, this paper introduces a simple metal cation-induced gelation method to prepare an electrocatalyst with PtNi alloy-NiO dual sites supported on Ti3C2Tx, which simultaneously exhibits excellent UOR and HER performance. PtNi-NiOx/Ti3C2Tx demonstrates good catalytic activity for the urea oxidation reaction, requiring only 1.364V (overpotential of 0.994V) to achieve a current density of 100mAcm-2 in UOR, and also exhibits remarkable catalytic activity in the hydrogen evolution reaction, with PtNi-NiOx/Ti3C2Tx achieving a current density of 10mAcm-2 in HER with only 24mV of overpotential. In the UOR//HER two-electrode electrolysis cell, it requires only 1.361 and 1.538V to reach current densities of 10 and 100mAcm-2, respectively. According to density functional theory (DFT) calculations, the dual active sites can intelligently adsorb the electron-donating/electron-withdrawing groups in urea molecules, activate chemical bonds, and thereby initiate urea decomposition.

Harnessing the Unconventional Cubic Phase in 2D LaNiO3 Perovskite for Highly Efficient Urea Oxidation

AbstractPhase engineering is a critical strategy in electrocatalysis, as it allows for the modulation of electronic, geometric, and chemical properties to directly influence the catalytic performance. Despite its potential, phase engineering remains particularly challenging in thermodynamically stable perovskites, especially in a 2D structure constraint. Herein, we report phase engineering in 2D LaNiO3 perovskite using the strongly non‐equilibrium microwave shock method. This approach enables the synthesis of conventional hexagonal and unconventional trigonal and cubic phases in LaNiO3 by inducing selective phase transitions at designed temperatures, followed by rapid quenching to allow precise phase control while preserving the 2D porous structure. These phase transitions induce structural distortions in the [LaO]+ layers and the hybridization between Ni 3d and O 2p states, modifying local charge distribution and enhancing electron transport during the six‐electron urea oxidation process (UOR). The cubic LaNiO3 offers optimal electron transport and active site accessibility due to its high structural symmetry and open interlayer spacing, resulting in a low onset potential of 1.27 V and a Tafel slope of 33.1 mV dec−1 for UOR, outperforming most current catalysts. Our strategy features high designability in phase engineering, enabling various electrocatalysts to harness the power of unconventional phases.

Harnessing the Unconventional Cubic Phase in 2D LaNiO3 Perovskite for Highly Efficient Urea Oxidation

AbstractPhase engineering is a critical strategy in electrocatalysis, as it allows for the modulation of electronic, geometric, and chemical properties to directly influence the catalytic performance. Despite its potential, phase engineering remains particularly challenging in thermodynamically stable perovskites, especially in a 2D structure constraint. Herein, we report phase engineering in 2D LaNiO3 perovskite using the strongly non‐equilibrium microwave shock method. This approach enables the synthesis of conventional hexagonal and unconventional trigonal and cubic phases in LaNiO3 by inducing selective phase transitions at designed temperatures, followed by rapid quenching to allow precise phase control while preserving the 2D porous structure. These phase transitions induce structural distortions in the [LaO]+ layers and the hybridization between Ni 3d and O 2p states, modifying local charge distribution and enhancing electron transport during the six‐electron urea oxidation process (UOR). The cubic LaNiO3 offers optimal electron transport and active site accessibility due to its high structural symmetry and open interlayer spacing, resulting in a low onset potential of 1.27 V and a Tafel slope of 33.1 mV dec−1 for UOR, outperforming most current catalysts. Our strategy features high designability in phase engineering, enabling various electrocatalysts to harness the power of unconventional phases.

Membrane-Free Water Electrolysis for Hydrogen Generation with Low Cost.

Conventional water electrolysis relies on expensive membrane-electrode assemblies and sluggish oxygen evolution reaction (OER) at the anode. Here, we develop an innovative and efficient membrane-free water electrolysis system to overcome these two obstacles simultaneously. This system utilizes the thermodynamically more favorable urea oxidation reaction (UOR) to generate clean N2 over a new class of Cu-based catalyst (CuXO), fundamentally eliminating the explosion risk of H2 and O2 mixing while removing the need for membranes. Notably, this membrane-free electrolysis system exhibits the highest H2 Faradaic efficiency among reported membrane-free electrolysis work. In situ spectroscopic studies reveal that the new N2Hy intermediate-mediated UOR mechanism on the CuXO catalyst ensures its unique N2 selectivity and OER inertness. More importantly, an industrial-type membrane-free water electrolyser (MFE) based on this system successfully reduces electricity consumption to only 3.87 kWh Nm-3, significantly lower than the 5.17 kWh Nm-3 of commercial alkaline water electrolyzers (AWE). Comprehensive techno-economic analysis (TEA) suggests that the membrane-free design and reduced electricity input of the MFE plants reduce the green H2 production cost to US$1.81 kg-1, which is lower than those of grey H2 while meeting the technical target (US$2.00-2.50 kg-1) set by European Commission and United States Department of Energy.

Membrane‐Free Water Electrolysis for Hydrogen Generation with Low Cost

Conventional water electrolysis relies on expensive membrane‐electrode assemblies and sluggish oxygen evolution reaction (OER) at the anode. Here, we develop an innovative and efficient membrane‐free water electrolysis system to overcome these two obstacles simultaneously. This system utilizes the thermodynamically more favorable urea oxidation reaction (UOR) to generate clean N2 over a new class of Cu‐based catalyst (CuXO), fundamentally eliminating the explosion risk of H2 and O2 mixing while removing the need for membranes. Notably, this membrane‐free electrolysis system exhibits the highest H2 Faradaic efficiency among reported membrane‐free electrolysis work. In situ spectroscopic studies reveal that the new N2Hy intermediate‐mediated UOR mechanism on the CuXO catalyst ensures its unique N2 selectivity and OER inertness. More importantly, an industrial‐type membrane‐free water electrolyser (MFE) based on this system successfully reduces electricity consumption to only 3.87 kWh Nm−3, significantly lower than the 5.17 kWh Nm−3 of commercial alkaline water electrolyzers (AWE). Comprehensive techno‐economic analysis (TEA) suggests that the membrane‐free design and reduced electricity input of the MFE plants reduce the green H2 production cost to US$1.81 kg−1, which is lower than those of grey H2 while meeting the technical target (US$2.00–2.50 kg−1) set by European Commission and United States Department of Energy.

A Rechargeable Urea‐Assisted Zn‐Air Battery With High Energy Efficiency and Fast‐Charging Enabled by Engineering High‐Energy Interfacial Structures

AbstractElectrochemical urea oxidation reaction (UOR) offers a promising alternative to the oxygen evolution reaction (OER) in clean energy conversion and storage systems. Nickel‐based catalysts are regarded as highly promising electrocatalysts for the UOR. However, their effectiveness is significantly hindered by the unavoidable self‐oxidation reaction of nickel species during UOR. To address this challenge, we proposed an interface chemistry modulation strategy to boost UOR kinetics by creating a high‐energy interfacial heterostructure. This heterostructure incorporates Ag at the CoOOH@NiOOH heterojunction interface, where strong interactions significantly promote the electron exchanges at the heterojunction interface between ‐OH and ‐O groups. Consequently, the improved electron delocalization leads to the formation of stronger bonds between Co sites and urea CO(NH2)2, promoting a preference for urea to occupy Co active sites over OH*. The resulting catalyst, Ag−CoOOH@NiOOH, demonstrates ultrahigh UOR activity with a low potential of 1.33 V at 100 mA cm−2. The fabricated catalyst exhibits a mass activity over 11.9 times greater than the initial cobalt oxyhydroxide. The rechargeable urea‐assisted zinc‐air batteries (ZABs) achieve a record‐breaking energy efficiency of 74.56 % at 1 mA cm−2, remarkable durability (1000 hours at a current density of 50 mA cm−2), and quick charge performances.

A Rechargeable Urea-Assisted Zn-Air Battery With High Energy Efficiency and Fast-Charging Enabled by Engineering High-Energy Interfacial Structures.

Electrochemical urea oxidation reaction (UOR) offers a promising alternative to the oxygen evolution reaction (OER) in clean energy conversion and storage systems. Nickel-based catalysts are regarded as highly promising electrocatalysts for the UOR. However, their effectiveness is significantly hindered by the unavoidable self-oxidation reaction of nickel species during UOR. To address this challenge, we proposed an interface chemistry modulation strategy to boost UOR kinetics by creating a high-energy interfacial heterostructure. This heterostructure incorporates Ag at the CoOOH@NiOOH heterojunction interface, where strong interactions significantly promote the electron exchanges at the heterojunction interface between -OH and -O groups. Consequently, the improved electron delocalization leads to the formation of stronger bonds between Co sites and urea CO(NH2)2, promoting a preference for urea to occupy Co active sites over OH*. The resulting catalyst, Ag-CoOOH@NiOOH, demonstrates ultrahigh UOR activity with a low potential of 1.33 V at 100 mA cm-2. The fabricated catalyst exhibits a mass activity over 11.9 times greater than the initial cobalt oxyhydroxide. The rechargeable urea-assisted zinc-air batteries (ZABs) achieve a record-breaking energy efficiency of 74.56 % at 1 mA cm-2, remarkable durability (1000 hours at a current density of 50 mA cm-2), and quick charge performances.

Rational Design of Ultrahigh-Loading Ir Single Atoms on Reconstructed Mn─NiOOH for Enhanced Catalytic Performance in Urea-Water Electrolysis.

Investigating advanced electrocatalysts is crucial for improving the efficacy of water splitting to generate environmentally friendly fuel. The discovery of highly effective electrocatalysts, capable of driving oxygen evolution reaction (OER) and urea oxidation reaction (UOR) in urea-alkaline environments, is pivotal for advancing large-scale hydrogen production. This study aims to introduce a new method that involves creating nanosheets of high-loading iridium single atoms embedded in a manganese-containing nickel oxyhydroxide matrix (Ir@Mn─NiOOH). These nanostructures are derived from self-supported hydrate pre-catalyst nanosheets grown on nickel foam and then activated through electrochemical etching pretreatment. The Ir@Mn─NiOOH nanoarchitecture displays outstanding electrocatalytic activity, having a low overpotential of just 258mV and a potential of 1.319V (at 10mAcm-2) for OER and UOR, respectively. Such extraordinary catalytic characteristics of Ir@Mn─NiOOH is mainly owing to the strong synthetic electronic interaction between Ir single atoms and Mn─NiOOH, which can change its electronic characteristics and boost electrochemical catalytic sites. This research presents a new way to produce exceptionally efficient catalysts by adding a synergistic effect to complex multi-electron processes.

Nickel Hydroxysulfide Electrocatalyst Promotes Urea Oxidation for Energy‐Saving Hydrogen Production

AbstractThe occurrence of oxygen evolution reaction (OER) almost consumes most of the electric energy of hydrogen production by electrocatalytic water splitting. The energy required in the process of electrochemical hydrogen production can be reduced by choosing urea oxidation reaction (UOR) instead of OER. In this work, nickel hydroxysulfide is synthesized on nickel foam (NiSOH/NF) and its electrocatalytic performance was tested in UOR. Experimental results show that the vulcanization catalyst requires a low potential of 1.38 V (vs RHE) to achieve a current density of 100 mA cm−2 in an electrolyte containing 0.5 M urea, which is 270 mV lower than the conventional OER process. This innovative approach has yielded a substantial reduction in the cell voltage necessary for overall water splitting under two electrode system, thereby enhancing its efficiency and feasibility.

Triphenylamine-Substituted Ni(II) Porphyrins for Urea Electro-oxidation.

Porphyrin-based molecular catalysts possess a typical aromatic macrocyclic structure regarding their metal centers and coordination frameworks, allowing for the development of promising electrocatalysts through precise selection of the metal and porphyrin ligand. However, reports on metalloporphyrins as catalysts for the electrocatalytic urea oxidation reaction (UOR) remain scarce. With these considerations in mind, the triphenylamine-Ni(II) porphyrin (NiPor-TPA) was synthesized through the solvothermal approach from 5,10,15,20-tetrakis [4-(diphenylamino)phenyl]porphyrin and nickel(II) acetate in this work. Experimental results reveal that the introduction of Ni species can serve as active sites and activate urea oxidation efficiently, and thus the prepared catalysts deliver better electrocatalytic activity than the metal-free TPA. The NiPor-TPA electrode delivers the lowest potential of 1.34 V versus reversible hydrogen electrode (RHE) at 10 mA cm-2 for UOR with a Tafel slope of 44.6 mV dec-1. This work proposes a new porphyrin-based molecular catalyst for effectively boosting electrocatalytic UOR activity. The π-conjugated macroring structure and the excellent electrocatalytic properties both make NiPor-TPA one of the burgeoning electrocatalytic UORs.